Globally increasing energy demands and environmental concerns related to the use of fossil fuels have stimulated extensive research to identify new energy systems and economies that are sustainable, clean, low cost, and environmentally benign. Hydrogen generation from solar-driven water splitting is a promising strategy to store solar energy in chemical bonds. The subsequent combustion of hydrogen in fuel cells produces electric energy, and the only exhaust is water. These two reactions compose an ideal process to provide clean and sustainable energy. In such a process, a hydrogen evolution reaction (HER), an oxygen evolution reaction (OER) during water splitting, and an oxygen reduction reaction (ORR) as a fuel cell cathodic reaction are key steps that affect the efficiency of the overall energy conversion. Catalysts play key roles in this process by improving the kinetics of these reactions. Porphyrin-based and corrole-based systems are versatile and can efficiently catalyze the ORR, OER, and HER. Because of the significance of energy-related small molecule activation, this review covers recent progress in hydrogen evolution, oxygen evolution, and oxygen reduction reactions catalyzed by porphyrins and corroles.
Herein we demonstrate that an external electric field (EEF) acts as an accessory catalyst/inhibitor for Diels-Alder (DA) reactions. When the EEF is oriented along the "reaction axis" (the coordinate of approach of the reactants in the reaction path), the barrier of the DA reactions is lowered by a significant amount, equivalent to rate enhancements by 4-6 orders of magnitude. Simply flipping the EEF direction has the opposite effect, and the EEF acts as an inhibitor. Additionally, an EEF oriented perpendicular to the "reaction axis" in the direction of the individual molecule dipoles can change the endo/exo selectivity, favouring one or the other depending on the positive/negative directions of the EEF vis-à-vis the individual molecular dipole. At some critical value of the EEF along the "reaction axis", there is a crossover to a stepwise mechanism that involves a zwitterionic intermediate. The valence bond diagram model is used to comprehend these trends and to derive a selection rule for EEF effects on chemical reactions: an EEF aligned in the direction of the electron flow between the reactants will lower the reaction barrier. It is shown that the exo/endo control by the EEF is not associated with changes in secondary orbital interactions.
"Give us insight, not numbers" was Coulson's admonition to theoretical chemists. This Review shows that the valence bond (VB)-model provides insights and some good numbers for one of the fundamental reactions in nature, the hydrogen-atom transfer (HAT). The VB model is applied to over 50 reactions from the simplest H + H(2) process, to P450 hydroxylations and H-transfers among closed-shell molecules; for each system the barriers are estimated from raw data. The model creates a bridge to the Marcus equation and shows that H-atom abstraction by a closed-shell molecule requires a higher barrier owing to the additional promotion energy needed to prepare the abstractor for H-abstraction. Under certain conditions, a closed-shell abstractor can bypass this penalty through a proton-coupled electron transfer (PCET) mechanism. The VB model links the HAT and PCET mechanisms conceptually and shows the consequences that this linking has for H-abstraction reactivity.
The water-soluble cationic nickel(II) complex of meso-tetrakis(4-N-methylpyridyl)porphyrin (1) can electrocatalyze water oxidation to O2 in neutral aqueous solution (pH 7.0) with the onset of the catalytic wave appearing at ∼1.0 V (vs NHE). The homogeneous catalysis with 1 was verified. Catalyst 1 exhibited water oxidation activity in a pH range 2.0-8.0 and had a strict linear dependence of catalytic current on its concentration. After 10 h of constant potential electrolysis at 1.32 V (vs NHE), a negligible difference of the solution was observed by UV-vis. In addition, inspection of the working electrode by electrochemistry, scanning electron microscope (SEM), and energy dispersive X-ray spectroscopy (EDX) showed no sign of deposition of NiOx films. These results strongly argued that 1 is a real molecular electrocatalyst for water oxidation. The turnover frequency (TOF) for this process was 0.67 s(-1) at 20 °C. On the basis of results from the kinetic isotope effect (KIE) and inhibition experiments, electrochemical studies in various buffer solutions with different anions and pHs, and DFT calculations, a catalytic cycle of 1 for water oxidation via a formally Ni(IV) species was proposed.
Six cobalt and manganese corrole complexes were synthesized and examined as single-site catalysts for water splitting. The simple cobalt corrole [Co(tpfc)(py)2] (1, tpfc = 5,10,15-tris(pentafluorophenyl)corrole, py = pyridine) catalyzed both water oxidation and proton reduction efficiently. By coating complex 1 onto indium tin oxide (ITO) electrodes, the turnover frequency for electrocatalytic water oxidation was 0.20 s(−1) at 1.4 V (vs. Ag/AgCl, pH = 7), and it was 1010 s(−1) for proton reduction at −1.0 V (vs. Ag/AgCl, pH = 0.5). The stability of 1 for catalytic oxygen evolution and hydrogen production was evaluated by electrochemical, UV-vis and mass measurements, scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX), which confirmed that 1 was the real molecular catalyst. Titration and UV-vis experiments showed that the pyridine group on Co dissociated at the beginning of catalysis, which was critical to subsequent activation of water. A proton-coupled electron transfer process was involved based on the pH dependence of the water oxidation reaction catalyzed by 1. As for manganese corroles 2–6, although their oxidizing powers were comparable to that of 1, they were not as stable as 1 and underwent decomposition at the electrode. Density functional theory (DFT) calculations indicated that water oxidation by 1 was feasible through a proposed catalytic cycle. The formation of an O–O bond was suggested to be the rate-determining step, and the calculated activation barrier of 18.1 kcal mol(−1) was in good agreement with that obtained from experiments.
Dopamine can be generated from tyramine via arene hydroxylation catalyzed by a cytochrome P450 enzyme (CYP2D6). Our quantum mechanical/molecular mechanical (QM/MM) results reveal the decisive impact of the protein in selecting the 'best' reaction mechanism. Instead of the traditional Meisenheimer-complex mechanism, the study reveals a mechanism involving an initial hydrogen atom transfer from the phenolic hydroxyl group of the tyramine to the iron-oxo of the compound I (Cpd I), followed by a ring-π radical rebound that eventually leads to dopamine by keto-enol rearrangement. This mechanism is not viable in the gas phase since the O-H bond activation by Cpd I is endothermic and the process does not form a stable intermediate. By contrast, the in-protein reaction has a low barrier and is exothermic. It is shown that the local electric field of the protein environment serves as a template that stabilizes the intermediate of the H-abstraction step and thereby mediates the catalysis of dopamine formation at a lower energy cost. Furthermore, it is shown that external electric fields can either catalyze or inhibit the process depending on their directionality.
This letter reports a computational study of methane hydrogen abstraction (HAT) process by several nonheme high-valent iron(IV)-oxo model oxidants, in the quintet and triplet spin states, employing coupled-cluster (RCCSD(T)) and density functional theory (DFT) methods. The exchange-enhanced HAT reactivity of the quintet state found previously by B3LYP calculations is confirmed in this work by means of the RCCSD(T) calculations. In addition, we benchmark herein 29 functionals against the RCCSD(T) results. It is found that B3LYP gives very good triplet-state transition state (TS) geometries, while its quintet-state TS is early relative to RCCSD(T). TPSSh and M06L perform well in TS geometry optimization. However, all 29 tested DFT methods underestimate the quintet-state HAT barriers, and most of them underestimate the triplet-state HAT barriers as well. Although B3LYP, B3LYP-D, and TPSSh underestimate both quintet- and triplet-state barriers, their barriers, and quintet-triplet differences thereof, in a series of reactions correlate extremely well with the corresponding RCCSD(T) quantities.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
334 Leonard St
Brooklyn, NY 11211
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.